Alkyl 3-acyloxy-2-alkenoates and homopolymers thereof



United States Patent "ice 3,129,201

Patented Apr. 14, 1964 r I a or the ethyl or isopropyl 4-ethyl Z-pentynoate, the alkyl 3,129,201 2-hexynoates such as methyl or propyl Z-hexynoate; the

ALKYL 3-ACYLQXY-2-ALKENOATES AND arylpropiolates such as ethyl or amyl phenylpropiolate HUMQ YME S TKLEREOF or 2-, 3-, or 4-tolylpropiolate and methyl or butyl Daywfi, @hi9 a5gm3r t0 Monsams 5 5 a-naphthylpropiolate; the alkyl 2-heptynoates such as ethyl i5 gg Laws Cowman of or butyl Z-heptynoate or methyl and methyl or isobutyl Na railing. Filed Oct. so, 1%9,Ser. No. 849,721 s'methyl z'hiptymaiei the alkyl z'wymates Such as 19 (112mg ((11. methyl or propyl 2-octynoate, etc.

Examples of compounds prepared according to the The present invention relates to olefinic diesters and Presently Provided Precess fife, -3 methyl, ethyl, more particularly provides an improved process of preamyl 3'benzoyloxyacryldlei ethyl, P py P y paring alkyl 3-acyloxy-2-alkenoates, especially the alkyl 3'acemxyaclylflte; butyL lsoamyl methyl -P P Y' 3-acyloxyacrylates. The invention also provides certain oxyacrylate; lsobutyl, m t yl or ethyl 3-acry1oyloxyvaluable and hitherto unknown esters of 3-hydroxyacrylic acrylate; Infithyl, ethyl or l opropyl 3pr0penoyloxyacryacid. According to the invention the alkyl 3-acy1oxy. 5 late; amyl, propyl or butyl 3-butyroyloxyacrylate; methyl, alkenoates are prepared by the catalyzed addition reaction ethyl butyl 0T Y l/) S/ of an acetylenic carboxylic acid, say, alkyl Z-alkynoate ethyh {methyl or P PY Y Y Y twith a monocarboxylic acid having a hydrogen ion conamyl, P PY or m yl -d pnenylacctoxyacrylate; centration of less than l.3 96 10 The reaction takes ethyl methyl: P PY 0T Q' P Y YM Y place Substantially according to the Schema; butyl, amyl or ethyl 3-(2- or 4-n1trobenzoylo-xy)acrylate; ethyl, methyl or amyl 3-(2-, 3-, or 4-phenoxybenzoyloxy)- 0 Z 0 O 0 acrylate; ethyl, isoamyl or propyl 3-(3-phenylpropionyl- 1 g RQLJOCZIOHPWY oxy)acrylate; ethyl, methyl or isobutyl 3-(2-hexenoyloxy)- acrylate; ethyl, methyl or isoamyl 3-(2-furoyloxy)acrywhere R is a radical corresponding to the carboxy-free late; isopropyl, amyl or methyl 3-(2-, 3-, or 4-toluoyloxy)- residue of a carboxylic acid having an ionization constant acrylate; ethyl, methyl or propyl 3-(3-butenoyloxy)acry- 3f less than 1396x10 Y is an alkyl radical of from late; propyl, butyl or methyl 3-dodecanoyloxyacrylate; l to 5 carbon atoms, and Z is selected from the class methyl, butyl or isoamyl 3-(2-hexenoyloxy)acrylate, consisting of Y, hydrogen, and aryl radicals of from methyl or ethyl 3-acetoxy-2-butenoate; methyl or butyl 6 to 10 carbon atoms. 3-benzoyloxy-2-butenoate; butyl or amyl 3-acryloyloxy- Examples of presently useful carboxylic acids, i.e., Z-butenoate; methyl or ethyl 3-propionyloxy-Z-pentenoate,

those having an ionization constant of less l.396 10 butyl or methyl 3-(2-naphthoyloxy)-2-butenoate, amyl are the alkanecarboxylic acids, the alkenecarboxylic acids or butyl 3-butyroxy-2-pentenoate, methyl or ethyl 3-(4- and the aromatic hydrocarbon carboxylic acids broadly. toluoyloxy)Z-pentenoate, amyl or isopropyl 3-acetoxy- Substituents may be present at the aliphatic chain and/ or Z-hexenoate, ethyl or methyl 3-(9-fiuorenoyloxy)-2- the aromatic nucleus of the carboxylic acid so long as hexenoate, amyl or methyl 3-(4-chlorobenzoyloxy)-2- the ionization constant of the acid is not greater than hexenoate, ethyl or methyl 3-(3-butenoyloxy)-2-hexenoate, that of chloroacetic acid, i.e., 1396x10 Such submethyl or ethyl 3-acetoxy Z-heptenoate, butyl or isopropyl stituents may be, e.g., halogen, nitro, alkoxy, hydroxy, 3-(4-ethylbenzoyloxy)-2-heptenoate, butyl or propyl aldehyde, carboalkoxy, amido, etc. The carboxylic acid 3-propionyloxy-2-octenoate, methyl or ethyl 3-cinnarnoylmay also be a cycloaliphatic acid or a heterocyclic acid oxy-2-octenoate, methyl or ethyl 3-acetoxy-3-phenylacryhaving the above specified hydrogen ion concentration. late, ethyl or isopropyl 3-propionyloxy-3-phenylacrylate,

Examples of the individual carboxylic acids which are methyl or butyl 3-acetoxy-3-(2-tolyl)acrylate, ethyl or useful for the present purpose are acetic acid, propionic propyl 3-acetoxy 3-(4-ethylphenyl)acrylate, methyl or acid, heptanoic acid, octanoic acid, decanoic acid, ethyl S-propionyloxy 3-(B-naphthyl)acry1ate, ethyl or dodecanoic acid, stearic acid, benzoic acid, butyric or propyl 3-acetoxy-3-(a-naphthyD-acrylate, butyl or methyl isobutyric acid, caproic acid, caprylic acid, 2-ch1oro- 3-(9-fluorenoyloxy)-3-phenylacrylate.

H C a 4-Ch10f0benZ0iC acid, 4-Ch10f0- The presently provided process is particularly valuable Cinnamic a id, 2-, 3- r 4-ch1o op e y1a ic acid, 0 in that it provides as new compounds the hitherto S-chloropropionic acid, acrylic acid, 3-butenoic ac d, unknown alkenoyloxyacrylates, i.e., compounds of the cinnamic acid, 3,3-dimethylacrylic acid, diphenylacetic t t acid, 2,4-dinitrophenylacetic acid, 4-ethylbenzoic acid, 4-ethylphenylacetic acid, 2-, 3-, or 4-fluorobenzoic acid,

H H formic acid, 2-, 3-, or 4-hydroxybenzoic acid, 2-iodo- MkQDYICOCHZCHCOY benzoic acid, 2-, 3- or 4-niethoxybenzoic acid, 2-isopropylwherein alkenyl designates an alkenyl radical of from l-naphthoic acid, lor Z-naphthoic acid, 3- or 6-rnethoxy- 2 to 6 carbon atoms and Y is an alkyl radical of from 1 Z-naphthoic acid, 2- or 4-nitrobenzoic acid, 2-, 3-, or o 5 carbon atoms. These compounds are prepared 4-nitrocinnamic acid, 2-nitro-3-phenylpropionic acid, 2-, according to the invention by the reaction of an alkenoic 3-, or 4-phenoxybenzoic acid, Z-phenylbenzoic acid, acid having from 2 to 6 carbon atoms with the alkyl ll-dodecenoic acid, octadecenoic acid, Z-hexenoic acid, P P The alkyl Y Y -W thus Obtained 4-methyl-2-pentenoic acid, 3-propylidenepropionic acid, polymerize to tough, rubbery Solids p Standing at pyridine-2-carboxylic acid, pyridine-El-carboxylic acid, room temperature or heating at, say, a temperature of pyridine-4-carboxylic acid, Z-furoic acid, 2-, 3-, or 4-toluic from to The polymefilation y be acid, valeric and isovaleric acid, vanillic acid, 1-, 2-, 3-, accelerated, if desired, by the use of free radical-liberating 4-, or 9-flu0renecarboxylic acid. agents, e.g., peroxidic compounds such as benzoyl peroxide The presently useful alkyl alkynoates are for example, or tert-butyl hydroperoxide, etc. the alkyl propiolates such as the methyl, ethyl, propyl, Solutions of the present homopolymeric alkyl, 3-alisopropyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, r kenoyloxy-acrylates are useful as coatings and give flextert-arnyl propiolates; the alkyl tetrolates such as the ible films upon casting. This class of compounds is also methyl, ethyl, propyl, butyl or amyl tetrolates; the alkyl valuable as copolymerizing monomers with, e.g., vinyl 2 pentynoatcs such as the methyl or butyl Z-pentynoate compounds such as the alkyl acrylates and methacrylates reacting metallic =3) or the vinyl aromatic compounds such as styrene or amethylstyrene. They also serve as cross-linking agents in the manufacture of hard resins of very good mechanical properties from linear polyesters, polymeric diolefins, etc. They are also advantageously employed as biological toxicants, e.g., as bactericides, fungicides, insecticides, and as nematocides.

The invention also provides as new and valuable compounds the alkyl 3-acyloxyacrylates wherein the acyl radical is derived from a naphthoic acid or from a fluorenecarboxylic acid. The alkyl 3-naphthoyloxyacrylates are valuable as microbiological toxicants and as soil fungicides and the alkyl 3-fluorenoyloxyacry1ates possess selective herbicide properties, and are particularly valuable for their preemergent elTect.

Reaction of the monocarboxylic acid with the alkyl alkanoates takes place in the presence of basic or acidic catalysts. Basic catalysts useful in the process include organic bases such as pyridine, the quaternary ammonium salts or bases such as trimethylbenzylammonium hydroxide, the alkali and alkali metal hydroxides or basically reacting salts thereof such as sodium, potassium, lithium, calcium, or magnesium hydroxide, carbonates or acetate; alkali or alkali metal alcoholates such as sodium methylate, etc. Examples of useful acidic catalysts are acid salts, such as cuprous or cupric, stannous or stannic, ferrous or ferric acetates, sulfates or chlorides, organic or inorganic acids such as acetic, sulfuric, phosphoric or oxalic acid, etc. While I prefer to use as a catalyst a material which is soluble in the mixture of carboxylic acid and propiolate, such solubility of the catalyst in the initial reactants is not a necessary property of the catalyst.

According to the invention the 3-acyloxyalkenoates are readily prepared by simply mixing the carboxylic acid with the alkynoate in the presence of either the acidic or basic catalyst and in the presence or absence of an inert diluent or solvent and allowing the resulting reaction mixture to stand at ordinary or increased temperatures until formation of the 3-acyloxyalkenoate has occurred. Useful solvents or diluents are, e.g., benzene, xylene, dioxane, dichlorobenzene or hexane. Depending on the nature of the individual carboxylic acid and of the catalyst employed, the addition reaction may occur under varying conditions of temperature and pressure. For optimum yields, it is advantageous to heat the reaction mixture at temperatures of, say, from approximately 60 C. to the refluxing temperature of the reaction mixture.

Inasmuch as molecular equivalents of the carboxylic acid and the alkynoate are involved in the formation of the 3-acyloxy-2-a1kenoates, it is advantageous to employ stoichiometric proportions of the two reactants. If desired, however, any excess of either reactant may be employed since any unreacted material is readily separated from the product.

The alkyl 3-acyloxy-2-alkenoates are stable, rather highboiling, viscous liquids or crystalline materials which are separated from the reaction mixture, in the event that there has been employed either an excess of one of the reactants or a diluent, by methods known to those skilled in the art, e.g., by fractional distillation, crystallization, etc.

The present invention is further illustrated by, but not limited to, the following examples.

Example 1 This example describes reaction of methyl propiolate with acetic acid to give methyl 3-acetoxyacrylate. Reaction was effected by heating at reflux a mixture consisting of 12.0 g. (0.2 mole) of 99.7% glacial acetic acid, 16.8

g. (0.2 mole) of methyl propiolate, 100 ml. of benzene acrylate, B.P. 41-43 C./0.3 mm., n 1.4489, and analyzing as follows:

Found Cnlcd. for

Percent C 50.18 50.00 Percent ll 5. 74 5. 60

Infrared analyses of the compound confirmed the presence of both the structures.

Example 2 Found Calcd. for

Percent C 64. 44 04. 07 Percent H 4. 9G 4. 89

Example 3 This example describes the addition reaction of methyl propiolate with acrylic acid.

A mixture consisting of 9.2 g. (0.11 mole) of methyl propiolate, 7.2 g. (0.1 mole) of acrylic acid, 0.1 g. of hydroquinone, 2 drops of pyridine and 25 ml. of butanol was maintained under nitrogen in the absence of light at room temperature for 2 weeks. At the end of that time the reaction mixture was refluxed for 12 hours and evaporated at 70 C. under water pump vacuum. Distillation of the residue gave the substantially pure methyl 3-acryloyloxyacrylate, B.P. 54-55" C./0.1 mm., which analyzed 53.72% carbon and 5.29% hydrogen as against 53.84% and 5.16%, the respective calculated values. Infrared analyses showed the presence of the and the carboxylate groupings.

Example 4 A mixture consisting of 21.0 g. (0.1 mole) of 9-flu0renecarboxylic acid, 8.4 g. (0.1 mole) of methyl propiolate, 150 ml. of benzene and 1 ml. of pyridine was heated at reflux for 12 hours. At the end of that time the solvent was removed in vacuo to give as residue 22.1 g. (75% theoretical yield) of the substantially pure methyl 3-(9- fluorenoyloxy) acrylate.

Example 5 A mixture consisting of 9.2 g. (0.11 mole) of methyl propiolate, 17.2 g. (0.1 mole) of Z-naphthoic acid, ml. of benzene and 1 ml. of pyridine was stirred at reflux under nitrogen for 12 hours. The homogenous, deep red reaction mixture was evaporated to dryness to give a solid which upon recrystallization from absolute methanol gave the substantially pure methyl 3-(2-naphthoyloxy) acrylate, M.P. 8486 C. Repeated recrystallization from methanol gave the pure compound, M.P. 89-90 C., which analyzed 70.03% carbon and 4.98% hydrogen as against 70.30 and 4.72%, the respective calculated values.

Example 6 This example shows testing of the methyl 3-(2-naphthoyloxy)acry1ate of Example 5 as a soil fungicide. In this test method, naturally-infested soil fortified with fungi that incite root rots, stem cankers, seedling blights, and seed decay is treated with a test chemical and incubated in a sealed container for a period of 24 hours. Seeds are sowed in the treated soil which is then incubated at 70 F. for 48 hours before being removed to greenhouse benches. Disease assessments are made two weeks later.

A uniform supply of infested soil containing the following organisms was prepared.

Rhizocto nia solani Fusarium oxysporum f. vasinfectum Sclerotium rolfsii Verticillium albo-atrum Pythium ultl'mum A 6 ml. aliquot of a 1% stock solution of a test chemical is pipetted into a jar containing 600 g. of infested soil. This initial application rate is 100 ppm. or approm'mately 200 pounds per 6" acre. The jar is sealed and the contents thoroughly mixed by vigorous shaking. The treated soil is incubated at 70 C. and 24 hours later is transferred to 4" pots. Fifteen cotton and cucumber seeds are sowed in each pot. The seeded pots are then incubated at 70 F. and at a high relative humidity (96-98%) to assure activity of the organism in the soil. Forty-eight hours later the pots are removed to the greenhouse.

Two weeks later the number of seedlings emerged and the number remaining healthy are recorded. The percent emergence and disease incident is based on the inoculated, untreated and the sterile soil treatments. The following rating scale is used:

Employing the presently provided methyl 3-(2-naphthoyloxy)acrylate an excellent rating was thus obtained. Repetition of the testing at a 30 ppm. concentration also gave very good results.

Example 7 This example shows evaluation of the methyl 3-(9- fluorenoyloxy)acrylate of Example 4 as a preemergent herbicide. Briefly, the chemical is applied in spray form to soil seeded to representative grasses and broad-leaf plants.

Aluminum pans, 13 x 9" x 2", were filled with a good grade of top soil which had been screened through a A" wire mesh and mixed with sand in a preparation of two parts of the top soil to one part of the sand. The soil surface was then compacted to a depth of from the top of the pan. Twenty seeds each of wild oats, crab grass, rye grass, mustard and pigweed were then scattered on the soil surface and covered with soil to the pan top.

The present heribicidal solution was prepared by dissolving 0.4 g. of the methyl 3-(9-fluorenoyloxy)acrylate in 20 cc. of acetone. Ten m1. of this solution was diluted with water to 30 cc. Application of this quantity of the solution to said pans is calculated to correspond to the use of 25 lbs. of the test compound per acre. The planted pans were then placed in an exhaust hood and sprayed first with 30 cc. of an aqueous solution of a liquid fertilizer and 0.1% solution of octamethyl pyrophosphoramide. The liquid fertilizer was employed to give a uniform nutrition level and the amide was employed to prevent insect injury. Two pans were then respectively sprayed with the 25 lbs. per acre solution of the test compound. One of the pans which had been planted and treated with the liquid fertilizer and octamethyl pyrophosphoramide in the same manner was set aside to be used as a blank. The three pans were then placed in /2" of water and allowed to absorb moisture through perforated bottoms until the soil surface was completely moist. The pans were then transferred to a wet sand ench in the greenhouse, and maintained there for ten days under ordinary conditions of sunlight and watering. Observation of the pans at the end of that time showed that the pan which had been sprayed with the 25 lbs. per acre solution of the methyl 3-(9-fluorenoyloxy)acrylate indicated complete to very pronounced suppression of crab grass and pigweed; however, the wild oats, rye grass, and mustard had emerged and showed no evidence of phytotoxicity. Also, all of the seeds which had been planted in the pan which had not been sprayed with the methyl 3-(9-fluorenoyloxy)acrylate had emerged and the plants were in excellent condition. Accordingly, when used at the rate of 25 lbs. per acre, the methyl 3-(9- fluorenoyloxy)acrylate is an unusually effective preemergent herbicide in that it prevents emergence and growth of crab grass and pigweed without having any adverse efiect on wild oats, rye grass, and mustard.

Example 8 The methyl 3-acryloyloxyacrylate of Example 3 was alowed to stand overnight at room temperature in the absence of an inhibitor of polymerization. At the end of that time it was found to have been converted into the homopolymer, a tough rubbery solid. Application of a solution of the homopolymer in a volatile solvent to wood slats gave, upon volatilization of the solvent, a tenuous flexible coating.

What I claim is:

1. The process which comprises heating a mixture consisting essentially of an alkyl 2-alkynoate of the formula ZCECOOY where Y is alkyl of from 1 to 5 carbon atoms and Z is selected from the class consisting of Y, hydrogen and hydrocarbon aryl of from 6 to 10 carbon atoms, and a monocarboxylic acid having a hydrogen ion concentration of less than 1.396 10- an inert diluent and a basic catalyst, and recovering an alkyl 3-acyloxy-2-alkenoate of the formula 0 R(HJOCZ:CH(HJOY in which R is a radical corresponding to the carboxy-free residue of said carboxylic acid and Z and Y are as herein defined.

2. The process which comprises heating a mixture consisting essentially of an alkyl propiolate having from 1 to 5 carbon atoms in the alkyl, a monocarboxylic acid having a hydrogen ion concentration of less than l.396 10- an inert diluent and a basic catalyst and recovering an alkyl 3-acyloxyacrylate of the formula:

0 Ri'JoomoHi JoY wherein R is a radical corresponding to the carboxy-free residue of said carboxylic acid and Y is akyl of from 1 to 5 carbon atoms.

3. The method which comprises heating, in the presence of a basic catalyst, an alkyl propiolate having from 1 to 5 carbon atoms in the alkyl radical with an alkanoic acid and recovering an alkyl 3-alcoy1oxyacrylate having from 1 to 5 carbon atoms in the alkyl radical.

4. The method which comprises heating in the presence of a basic catalyst an aromatic hydrocarbon carboxylic acid with an alkyl propiolate having from 1 to 5 carbon atoms in the alkyl radical and recovering an alkyl 3- aroyloxyacrylate having from 1 to 5 carbon atoms in the alkyl radical.

5. The method which comprises heating, in the presence of a basic catalyst, an alkene monocarboxylic acid having from 2 to 6 carbon atoms in the alkylene radical with an alkyl propiolate having from 1 to 5 carbon atoms in the alkyl radical and recovering an alkyl 3-alkenoyloxyacrylate having from 1 to 5 carbon atoms in the alkyl radical and from 2 to 6 carbon atoms in the alkcnoyl radical.

6. The process which comprises heating methyl propiolate with acetic acid in the presence of a basic catalyst and recovering methyl 3-acetoxyacrylate from the resulting reaction product.

7. The process which comprises heating methyl propiolate with benzoic acid in the presence of a basic catalyst and recovering methyl 3-benzoyloxyacrylate.

8. The process which comprises heating methyl propiolate with acrylic acid in the presence of a basic catalyst and recovering methyl 3-acryloyloxyacrylate.

9. The process which comprises heating methyl propiolate with 9-fluorenecarboxylic acid in the presence of a basic catalyst and recovering methyl 3-(9-fluorenoyl- 20 oxy) acrylate.

10. The process which comprises heating methyl propiolate with 2-naphthoic acid in the presence of a basic catalyst and recovering methyl 3-(2-naphthoyloxy)- acrylate.

11. An alkyl 3-alkenoyloxyacrylate having from 1 to 5 carbon atoms in the alkyl radical and from 2 to 6 carbon atoms in the alkenoyl radical.

12. The homopolymer of an alkyl 3-alkenoyloxyacrylate having from 1 to 5 carbon atoms in the alkyl radical and from 2 to 6 carbon atoms in the alkenoyl radical.

13. Methyl B-acryloyloxyacrylate.

14. Homopolymeric methyl 3-acryloyloxyacrylate.

15. An alkyl B-naphthoyloxyacrylate having from 1 to 5 carbon atoms in the alkyl radical.

16. Methyl 3-(2-naphthoyloxy)acrylate.

17. An alkyl 3-fluorenoyloxyacrylate having from 1 to 5 carbon atoms in the alkyl radical.

18. Methyl 3-(9-fiuorenoyloxy)acrylate.

19. A compound of the formula in which X is selected from the class consisting of alkenyl radicals of from 1 to 5 carbon atoms, and the naphthyl and fluorenyl radicals and Y is an alkyl radical of from 1 to 5 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS 2,141,546 Strain Dec. 27, 1938 2,521,914 Hagemeyer Sept. 12, 1950 2,540,073 Van Hook et a1 Jan. 30, 1951 2,594,827 Towne Apr. 29, 1952 2,599,424 Albrecht et al. June 3, 1952 OTHER REFERENCES Hanford et 211.: Ind. and Eng. Chem., vol. 40, pages 1171-1177 (1948).

UNITED PATENT OFF CE CERTIFICATE OF CORRECTION Patent No. 3,129,201 Q i pril 14, 1964 Le Miller l l I v l It is hereby certified that error appeai s "'in -theabove numbered natent requiring correction and that the Said Letters Patent should read as o'orrectedbelow. I

Column 2, lines 531 and 54, the-struCture should appear'as shown below instead of as in the patent;

alkenyl-COCH CHCbY' 4 Signed and sealed this 24th v O f- Allgl ls t 1965 SEAL) NEST w. SWIDER Y I EDWARD J. BRENNER lusting Officer I v Commissioner of Patents" 

1. THE PROCESS WHICH COMPRISES HEATING A MIXTURE CONSISTING ESSENTIALLY OF AN ALKYL 2-ALKYNOATE OF THE FORMYLA ZC$COOY WHERE Y IS ALKYL OF FROM 1 TO 5 CARBON ATOMS AND Z IS SELECTED FROM THE CLASS CONSISTING OF Y, HYDROGEN AND HYDROCARBON ARYL OF FROM 6 TO 10 CARBON ATOMS, AND A MONOCARBOXYLIC ACID HAVING A HYDROGEN ION CONCENTRATION OF LESS THAN 1.396X10-**3, ANINERT DILUENT AND A BASIC CATALYST, AND RECOVERING AN ALKYL 3-ACYLOXY-2-ALKENOATE OF THE FORMULA
 19. A COMPOUND OF THE FORMULA 